Monoazo dyes having a substituted 1,4-phenylene coupling component radical having one C8-14 alkyl group or moiety

ABSTRACT

A Monoazo compounds of the formula ##STR1## wherein D is a diazo component radical of the 4-nitrophenyl series, thienyl-2 series, thiazolyl-2 series or 5-nitrobenzoisothiazolyl-3 series, 
     R 1  is hydrogen; C 1-2  alkyl; C 1-2  alkoxy; formylamino; (C 1-4  alkyl)carbonylamino; (C 1-4  alkyl)carbonylamino the alkyl group of which is substituted by 1 to 3 substituents independently selected from halo, C 1-3  alkoxy, cyano, phenyl, phenoxy and benzyloxy; (C 2-4  alkenyl)carbonylamino; halo(C 2-4  alkenyl)carbonylamino; benzoylamino; benzoylamino the phenyl group of which is substituted by 1 to 3 substituents independently selected from halo, C 1-4  alkyl and C 1-4  alkoxy; (C 1-4  alkoxy)carbonylamino; (C 1-4  alkoxy)carbonylamino the alkyl moiety of which is substituted by 1 to 3 substituents independently selected from halo, C 1-3  alkoxy, cyano, phenyl, phenoxy and benzyloxy; (C 8-14  alkyl)carbonylamino or (C 8-14  alkoxy)carbonylamino, 
     R 2  is C 1-4  alkoxy or 2-(C 1-4  alkoxy)ethoxy, 
     R 3  is hydrogen, C 1-4  alkyl, C 8-14  alkyl, 2-(C 8-14  alkoxy)carbonylethyl, 2-(C 8-14  alkyl)carbonyloxyethyl or 2-(C 8-14  alkoxy)carbonyloxyethyl, and 
     R 4  is hydrogen, C 1-4  alkyl, 2-cyanoethyl, 2-(C 1-3  alkoxy)ethyl, 2-(C 1-4  alkyl)carbonyloxyethyl, 2-(C 1-4  alkoxy)carbonylethyl, 2-(C 1-4  alkoxy)carbonyloxyethyl, C 3-4  alkenyl, ##STR2##  C 8-14  alkyl, 2-(C 8-14  alkyl)-carbonyloxyethyl, 2-(C 8-14  alkoxy)carbonylethyl or 2-(C 8-14  alkoxy)carbonyloxyethyl, 
      wherein 
     R 5  is C 1-4  alkyl, allyl, (C 1-3  alkyl)-carbonyl, phenyl or phenyl substituted by 1 to 3 substituents independently selected from halo, C 1-2  alkyl and C 1-2  -alkoxy, and 
     R 6  is hydrogen, C 1-4  alkyl and (C 1-3  alkyl)-carbonyl, 
     with the proviso that one and only one of R 1 , R 3  and R 4  is or contains a C 8-14  alkyl group or moiety, 
     which are useful for dyeing textile materials, for example polyester.

The invention relates to monoazo dyes suitable for dyeing textile substrates, for example polyester.

According to the invention, there is provided a method for dyeing a textile substrate comprising applying to the substrate a compound of formula I ##STR3##

in which D is a diazo component radical of the 4-nitrophenyl series, thienyl-2series, thiazolyl-2 series or 5-nitrobenzisothiazolyl-3 series;

R₁ is hydrogen; C₁₋₂ alkyl; C₁₋₂ alkoxy; formylamino; C₁₋₄ alkylcarbonylamino in which the alkyl group can bear 1 to 3 groups independently selected from halogen, C₁₋₃ alkoxy, phenoxy, phenyl, benzyloxy and cyano; C₁₋₄ alkoxycarbonylamino in which the alkyl group can bear 1 to 3 groups independently selected from halogen, C₁₋₃ alkoxy, phenoxy, phenyl, cyano and benzyloxy; benzoylamino in which the phenyl group can bear 1 to 3 groups independently selected from halogen, C₁₋₄ alkyl and C₁₋₄ alkoxy; C₂₋₄ alkenylcarbonylamino; halo-C₂₋₄ alkenylcarbonylamino; C₈₋₁₄ alkylcarbonylamino or C₈₋₁₄ alkoxycarbonylamino;

R₂ is C₁₋₄ alkoxy (preferably C₁₋₂ alkoxy) or 2-(C₁₋₄ alkoxy)ethoxy (preferably 2-(C₁₋₂ alkoxy)ethoxy);

R₃ is C₈₋₁₄ alkyl, hydrogen, 2-C₈₋₁₄ alkoxycarbonylethyl, 2-C₈₋₁₄ alkylcarbonyloxyethyl, 2-C₈₋₁₄ alkoxycarbonyloxyethyl or C₁₋₄ alkyl; and

R₄ is hydrogen, C₁₋₄ alkyl, 2-cyanoethyl, C₃₋₄ alkenyl, 2-C₁₋₃ alkoxyethyl, 2-C₁₋₄ alkylcarbonyloxyethyl, 2-C₁₋₄ alkoxycarbonylethyl, C₈₋₁₄ alkyl, 2-C₁₋₄ alkoxycarbonyloxyethyl, 2-C₈₋₁₄ alkylcarbonyloxyethyl, 2-C₈₋₁₄ alkoxycarbonylethyl, 2-C₈₋₁₄ alkoxycarbonyloxyethyl or ##STR4##

wherein R⁵ is C₁₋₄ alkyl, allyl, C₁₋₃ alkylcarbonyl or phenyl, unsubstituted or substituted by 1 to 3 groups, independently selected from halogen C₁₋₂ alkyl and C₁₋₂ alkoxy, and

R₆ is hydrogen, C₁₋₄ alkyl or --COC₁₋₃ alkyl,

with the proviso that one and only one of R₁, R₃ and R₄ is or contains a C₈₋₁₄ alkyl group or moiety.

Unless otherwise indicated, each C₁₋₄ alkyl or C₈₋₁₄ alkyl group or moiety may be linear and branched and is preferably the former.

Any alkyl group and moiety in R₁ that may bear 1 to 3 substituents is preferably unsubstituted or monosubstituted, more preferably the former.

In this Specification any phenyl group is preferably unsubstituted or monosubstituted.

Any C₁₋₃ alkyl or C₁₋₄ alkyl group or moiety is preferably methyl or ethyl when unsubstituted. Any substituted C₁₋₄ alkyl group or moiety is preferably substituted C₁₋₃ alkyl when monosubstituted, substituted C₂₋₄ alkyl when disubstituted and substituted C₃₋₄ alkyl when trisubstituted. Any C₁₋₃ alkoxy or C₁₋₄ alkoxy group or moiety is preferably methoxy or ethoxy.

In this Specification, halogen is preferably fluoro, chloro or bromo, more preferably chloro or bromo.

Preferably D is D' where D' is a group of formula a, b, c, or d ##STR5##

in which R₇ is hydrogen, cyano or halogen;

one of R₈ and R₉ is hydrogen and the other is hydrogen or chloro (more preferably both R₈ and R₉ are hydrogen);

R₁₀ is cyano or nitro;

R₁₁ is hydrogen, halogen, C₁₋₄ alkyl or phenyl;

R₁₂ is formyl, cyano, nitro, C₁₋₄ alkoxycarbonyl or C₁₋₄ alkylcarbonyl;

R₁₃ is hydrogen, chloro, C₁₋₃ alkyl or phenyl; and

R₁₄ is cyano, nitro or C₁₋₄ alkoxycarbonyl.

More preferably D is D" where D" is a group of formula a' ##STR6##

in which R₇ ' is chloro or bromo.

Preferably R₁ is R₁ ' where R₁ ' is C₁₋₂ alkylcarbonylamino.

Preferably R₂ is R₂ ' where R₂ ' is C₁₋₂ alkoxy or 2-(C₁₋₂ alkoxy)ethoxy. More preferably R₂ is R₂ " where R₂ " is C₁₋₂ alkoxy.

Preferably when R₃ is hydrogen or C₁₋₄ alkyl, then R₄ is 2-C₈₋₁₄ alkoxycarbonylethyl.

More preferably R₃ is R₃ ' and R₄ is R₄ ' where R₃ ' is hydrogen or C₁₋₄ alkyl and R₄ ' is 2-C₁₀₋₁₂ alkoxycarbonylethyl or R₃ ' is C₁₀₋₁₂ alkyl and R₄ ' is hydrogen or allyl.

Compounds of formula I can be prepared by coupling a diazotised amine of formula II

    D--NH.sub.2                                                (II)

with a compound of formula III ##STR7##

Compounds of formulae II and III are known or may be prepared by known methods from known compounds. Diazotisation and coupling can be carried out by known methods.

Compounds of formula I are new.

Compounds of formula I can be worked up into dyeing preparations in known ways, for example by milling (e.g. sand milling) in the presence of a dispersing agent or filling material. The preparation so produced, which may be dried in vacuum or by atomisation, can be used in a long or a short dyebath for dyeing, padding or printing material.

The dyes of the invention exhaust very well (preferably at temperatures over 120° C., more preferably over 130° C.) to give deep shades on synthetic or semi-synthetic hydrophobic high molecular weight textile material from an aqueous suspension. The dyestuffs of the invention are particularly useful for dyeing, padding or printing textile material made from linear aromatic polyester, cellulose 21/2 acetate, cellulose triacetate or synthetic polyamide.

Dyeing, printing or padding may be carried out by known methods, in particular according to the methods described in UK Pat. No. 1,114,433 (=FP 1,445,371).

Compounds of formula I produce dyeings having excellent wet and contact fastness after thermal treatment (for example drying, after-fixing and finishing optionally in the presence of a finishing agent).

Besides having excellent wet and contact fastnesses, dyeings with compounds of formula I have generally good fastness properties.

The invention will now be illustrated by the following Examples in which all parts and percentages are by weight and all temperatures are in °C.

EXAMPLE 1

26.3 Parts of 2,4-dinitro-6-bromoaniline (99.6%) are dissolved in 130 parts of 94% sulphuric acid and are then diazotised at 15° to 20° C. with 36.5 parts of 40% nitrosylsulphuric acid.

42.9 Parts of 1-acetylamino-3-(2-n-dodecyloxycarbonylethyl) amino-4-methoxybenzene are dissolved in a mixture of 500 parts of glacial acetic acid and 70 parts of water. 2.5 Parts of aminosulphonic acid are added, the mixture is cooled to 0°-5° C. and the diazonium solution which has been cooled to 0°-5° C. is slowly added to the coupling component together with an even slower addition of 500 parts of water (at 0°-5° C.) whilst stirring well. The resulting dyestuff suspension is filtered, washed neutral with warm water and dried at about 50° C. under vacuum. The resultant dyestuff is of formula 1a ##STR8## (λmax in DMF=598 nm)

and dyes polyester a navy-blue shade with good fastness properties, in particular excellent wet and contact fastness properties after thermal aftertreatment.

The C₁₀₋₁₄ alkyl group or moiety of each compound of Examples 2-29 and 31-53 is linear, and the R₃ group of Example 30 is 1-methyl-n-undecyl. Each --C₂ H₄ -- radical in the examples is --(CH₂)₂ --.

EXAMPLES 2 TO 30

Compounds of the formula ##STR9##

in which R_(1a) to R₇ are as defined in Table 1 below, can be prepared by a method analogous to that of Example 1 from appropriate reactants.

                                      TABLE 1                                      __________________________________________________________________________                                                             Shades of              Ex.                                                 λmax.                                                                       dyeing on              No.                                                                               R.sub.7                                                                            R.sub.1a R.sub.2a                                                                              R.sub.3      R.sub.4         in nm                                                                              polyester              __________________________________________________________________________     2  Br  CH.sub.3 CH.sub.3                                                                              C.sub.2 H.sub.4 COOC.sub.10 H.sub.21                                                        H               598 navy blue              3  "   "        "      C.sub.2 H.sub.4 COOC.sub.14 H.sub.29                                                        H               598 "                      4  "   "        "      C.sub.2 H.sub.4 COOC.sub.10 H.sub.21                                                        C.sub.2 H.sub.5 607 greenish-blue          5  "   "        "      C.sub.2 H.sub.4 COOC.sub.12 H.sub.25                                                        "               607 "                      6  Cl  "        "      "            "               608 "                      7  "   "        "      "            H               599 navy blue              8  I   "        "      "            H               597 "                      9  "   "        "      "            C.sub.2 H.sub.5 606 greenish-blue          10 Br  "        C.sub.2 H.sub.5                                                                        ##STR10##   "               599 navy blue              11 "   "        "      "            H               599 "                      12 "   "        C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 COOC.sub.12 H.sub.25                                                        H               600 "                      13 "   "        "      "            C.sub.2 H.sub.5 609 greenish-blue          14 "   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                              "            H               599 navy blue              15 "   CH.sub.2Cl                                                                              "      "            H               596 "                      16 "   CH.sub.2OCH.sub.3                                                                       "      "            H               595 "                      17 "   CHCH.sub.2                                                                              "      "            H               601 "                      18 "   CH.sub.3 "      C.sub.10 H.sub.21                                                                           H               605 "                      19 "   "        "      C.sub.12 H.sub.25                                                                           CH.sub.2 CHCH.sub.2                                                                            612 greenish blue          20 "   "        "      C.sub.10 H.sub.21                                                                           C.sub.2 H.sub.4 CN                                                                             590 reddish-blue           21 "   "        "      "            CH.sub.2 CHCH.sub.2                                                                            612 blue                   22 "   C.sub.11 H.sub.23                                                                       "      CH.sub.2 CH.sub.3                                                                           C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                             609 "                      23 "   CH.sub.3 "      C.sub.10 H.sub.21                                                                           C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                                                             608 "                      24 "   "        "      "            C.sub.2 H.sub.4 OCOCH.sub.3                                                                    608 "                      25 "   "        "      "                                                                                            ##STR11##      607 "                      26 Br  CH.sub.3 CH.sub.3                                                                              C.sub.10 H.sub.21                                                                            ##STR12##      608 greenish-blue          27 "   "        "      "            C.sub.2 H.sub.4OCH.sub.3                                                                       614 "                      28 CN  "        "      C.sub.12 H.sub.25                                                                           H               624 blue-green             29 "   "        "      C.sub.10 H.sub.21                                                                           H               624 "                      30 "   "        "      CH(CH.sub.3)C.sub.10 H.sub.21                                                               H               625 "                      __________________________________________________________________________

EXAMPLES 31-35

The following compounds can be prepared by a method analogous to that of Example 1 from appropriate reactants

                                      TABLE 2                                      __________________________________________________________________________                                             Shades of                              Ex.                                 λmax.                                                                       dyeing on                              No.                                 in nm                                                                              polyester                              __________________________________________________________________________     31                                                                                 ##STR13##                       600 navy blue                              32                                                                                 ##STR14##                       590 "                                      33                                                                                 ##STR15##                       590 "                                      34                                                                                 ##STR16##                           blue                                   35                                                                                 ##STR17##                           navy blue                              __________________________________________________________________________

EXAMPLES 36-41

Compounds of the formula ##STR18##

in which R_(1a) to R₄ are defined in Table 3 below, can be prepared by a method analogous to that of Example 1 from appropriate reactants.

                                      TABLE 3                                      __________________________________________________________________________                                     Shade of                                       Ex.                         ═max.                                                                          dyeings on                                     No.                                                                               R.sub.1a                                                                           R.sub.2a                                                                            R.sub.3                                                                             R.sub.4    in nm                                                                              polyester                                      __________________________________________________________________________     36 --CH.sub.3                                                                         --CH.sub.3                                                                          H    --C.sub.2 H.sub.4 COOC.sub.12 H.sub.25                                                    608 navy blue                                      37 "   "    --C.sub.2 H.sub.5                                                                   "          628 greenish-                                                                      blue                                           38 "   --C.sub.2 H.sub.5                                                                   "    "          629 "                                              39 "   "    H    "          610 navy blue                                      40 "   --CH.sub.3                                                                          --C.sub.10 H.sub.21                                                                 --CH.sub.2 --CH═CH.sub.2                                                              631 greenish-                                                                      blue                                           41 "   --C.sub.2 H.sub.5                                                                   "    "          632 "                                              __________________________________________________________________________

EXAMPLES 42 to 53

Compounds of the formula ##STR19##

in which R_(2a), R₃, R₄, R₁₁ and R₁₄ are as defined in Table 4 below, can be prepared from appropriate reactants by a method analogous to that of Example 1. R₁₂ is --CN in Examples 42 to 51 and --CHO in Examples 52 and 53.

                                      TABLE 4                                      __________________________________________________________________________                                      Shade of                                      Ex.                              dyeing on                                     No.                                                                               R.sub.13                                                                           R.sub.14                                                                              R.sub.2a                                                                           R.sub.3                                                                             R.sub.4   polyester                                     __________________________________________________________________________     42 --CH.sub.3                                                                         --CN   --CH.sub.3                                                                         H    --C.sub.2 H.sub.4 COOC.sub.12 H.sub.25                                                   navy blue                                     43 "   "      "   --C.sub.2 H.sub.5                                                                   "         greenish-                                                                      blue                                          44 "   "      --C.sub.2 H.sub.5                                                                  "    "         "                                             45 "   "      "   H "  navy blue                                               46 --C.sub.6 H.sub.5                                                                  "      --CH.sub.3                                                                         H    "         "                                             47 "   "      --C.sub.2 H.sub.5                                                                  H    "         "                                             48 --CH.sub.3                                                                         --COOC.sub.2 H.sub.5                                                                  --CH.sub.3                                                                         H    "         "                                             49 "   "      "   --C.sub.2 H.sub.5                                                                   "         "                                             50 "   "      --C.sub.2 H.sub.5                                                                  "    "         "                                             51 "   "      "   H    "         "                                             52 C1  --CN   --CH.sub.3                                                                         --C.sub.10 H.sub.21                                                                 --CH.sub.2 --CH═CH.sub.2                                                             greenish-                                                                      blue                                          53 "   "      --C.sub.2 H.sub.5                                                                  "    "         "                                             __________________________________________________________________________

APPLICATION EXAMPLE

The dyestuff of formula 1a (prepared according to Example 1) is sandmilled in the presence of a commercially available ligninsulphonate (dispersing agent) followed by atomisation to form an ultradisperse dyeing preparation having an average particle size of 1μ and a coupage ratio of 3.5:10.

24 Parts of the above produced preparation are dispersed in 1000 parts of water and this is then added to 13,000 parts of a mother liquor containing 30 part of ammonium sulphate and 0.3 parts of formic acid as buffer (optionally with a carrier or levelling medium) at 60° C. in a dyeing autoclave. A pre-washed cross-bobbin (1000 parts of polyester yarn on a plastic frame) is added to the dyeing autoclave, which is then closed and heated over 35 minutes to 130° C. After 90 minutes, the autoclave is cooled to 80° C., the spent liquor is removed and the dyed substrate is washed thoroughly with cold water and then is reductively cleared.

After elimination of water, the substrate is dried. The resulting dyeing is of a navy blue nuance and is free of filtrations (i.e., impurities).

Instead of the compound of formula 1a an appropriate amount of any one of Examples 2 to 53 may be used in the method of the Application Example. 

What is claimed is:
 1. A process of dyeing a textile substrate comprising applying a compound of the formula ##STR20## to a textile substrate from an aqueous medium, whereinD is ##STR21## wherein R₇ is hydrogen, cyano or halo,R₈ is hydrogen or chloro, R₉ is hydrogen or chloro, with the proviso that at least one of R₈ and R₉ is hydrogen, R₁₀ is cyano or nitro, R₁₂ is formyl, cyano, nitro, (C₁₋₄ alkoxy)carbonyl or (C₁₋₄ alkyl)carbonyl, R₁₃ is hydrogen, chloro, C₁₋₃ alkyl or phenyl, and R₁₄ is cyano, nitro or (C₁₋₄ alkoxy)carbonyl, R₁ is hydrogen; C₁₋₂ alkyl; C₁₋₂ alkoxy; formylamino; (C₁₋₄ alkyl)carbonylamino; (C₁₋₄ alkyl)carbonylamino the alkyl group of which is substituted by 1 to 3 substituents independently selected from halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy and benzyloxy; (C₂₋₄ alkenyl)carbonylamino; halo(C₂₋₄ alkenyl)carbonylamino; benzoylamino; benzoylamino the phenyl group of which is substituted by 1 to 3 substituents independently selected from halo, C₁₋₄ alkyl and C₁₋₄ alkoxy; (C₁₋₄ alkoxy)carbonylamino; (C₁₋₄ alkoxy)carbonylamino the alkyl moiety of which is substituted by 1 to 3 substituents independently selected from halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy and benzyloxy; (C₈₋₁₄ alkyl)carbonylamino or (C₈₋₁₄ alkoxy)carbonylamino, R₂ is C₁₋₄ alkoxy or 2-(C₁₋₄ alkoxy)ethoxy, R₃ is hydrogen, C₁₋₄ alkyl, C₈₋₁₄ alkyl, 2-(C₈₋₁₄ alkoxy)carbonylethyl, 2-(C₈₋₁₄ alkyl)carbonyloxyethyl or 2-(C₈₋₁₄ alkoxy)carbonyloxyethyl, and R₄ is hydrogen, C₁₋₄ alkyl, 2-cyanoethyl, 2-(C₁₋₃ alkoxy)ethyl, 2-(C₁₋₄ alkyl)carbonyloxyethyl, 2-(C₁₋₄ alkoxy)carbonylethyl, 2-(C₁₋₄ alkoxy)carbonyloxyethyl, C₃₋₄ alkenyl, ##STR22## C₈₋₁₄ alkyl, 2-(C₈₋₁₄ alkyl)carbonyloxyethyl, 2-(C₈₋₁₄ alkoxy)carbonylethyl or 2-(C₈₋₁₄ alkoxy)carbonyloxyethyl, whereinR₅ is C₁₋₄ alkyl, allyl, (C₁₋₃ alkyl)carbonyl, phenyl or phenyl substituted by 1 to 3 substituents independently selected from halo, C₁₋₂ alkyl and C₁₋₂ alkoxy, and R₆ is hydrogen, C₁₋₄ alkyl or (C₁₋₃ alkyl)carbonyl, with the proviso that one and only one of R₁, R₃ and R₄ is or contains a C₈₋₁₄ alkyl group or moiety.
 2. A process according to claim 1 wherein D is ##STR23##
 3. A process according to claim 2 whereinD is ##STR24## wherein R₇ ' is chloro or bromo.
 4. A process according to claim 3 wherein the compound is applied to the textile substrate at a temperature above 120° C.
 5. A process according to claim 3 whereinR₁ is hydrogen; C₁₋₂ alkyl; C₁₋₂ alkoxy; formylamino; (C₁₋₄ alkyl)carbonylamino; (C₁₋₄ alkyl)carbonylamino the alkyl group of which is monosubstituted by halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy or benzyloxy; (C₂₋₄ alkenyl)carbonylamino; halo(C₂₋₄ alkenyl)carbonylamino; benzoylamino; benzoylamino the phenyl group of which is monosubstituted by halo, C₁₋₄ alkyl or C₁₋₄ alkoxy; (C₁₋₄ alkoxy)carbonylamino; (C₁₋₄ alkoxy)carbonylamino the alkyl moiety of which is monosubstituted by halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy or benzyloxy; (C₈₋₁₄ alkyl)carbonylamino or (C₈₋₁₄ alkoxy)carbonylamino, and R₅ is C₁₋₄ alkyl, allyl, (C₁₋₃ alkyl)carbonyl, phenyl or phenyl monosubstituted by halo, C₁₋₂ alkyl or C₁₋₂ alkoxy.
 6. A process according to claim 4 whereinR₁ is (C₁₋₂ alkyl)carbonylamino, and R₂ is C₁₋₂ alkoxy or 2-(C₁₋₂ alkoxy)ethoxy.
 7. A process according to claim 6 with the proviso that when one of R₃ and R₄ is hydrogen or C₁₋₄ alkyl, the other is 2-(C₈₋₁₄ alkoxy)carbonylethyl.
 8. A process according to claim 7 whereinR₃ is hydrogen or C₁₋₄ alkyl, and R₄ is 2-(C₁₀₋₁₂ alkoxy)carbonylethyl, or R₃ is C₁₀₋₁₂ alkyl, and R₄ is hydrogen or allyl.
 9. A process according to claim 8 wherein the compound is applied to the textile substrate at a temperature above 120° C.
 10. A process according to claim 9 wherein the textile substrate comprises a linear aromatic polyester, cellulose 21/2 acetate, cellulose triacetate or a synthetic polyamide.
 11. A process according to claim 10 wherein the textile substrate comprises a linear aromatic polyester.
 12. A process according to claim 7 wherein the compound is ##STR25##
 13. A textile substrate having applied thereto a monoazo compound of the formula ##STR26## wherein D is a diazo component radical of the 4-nitrophenyl series or the thienyl-2 series,R₁ is hydrogen; C₁₋₂ alkyl; C₁₋₂ alkoxy; formylamino; (C₁₋₄ alkyl)carbonylamino; (C₁₋₄ alkyl)carbonylamino the alkyl group of which is substituted by 1 to 3 substituents independently selected from halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy and benzyloxy; (C₂₋₄ alkenyl)carbonylamino; halo(C₂₋₄ alkenyl)carbonylamino; benzoylamino; benzoylamino the phenyl group of which is substituted by 1 to 3 substituents independently selected from halo, C₁₋₄ alkyl and C₁₋₄ alkoxy; (C₁₋₄ alkoxy)carbonylamino; (C₁₋₄ alkoxy)carbonylamino the alkyl moiety of which is substituted by 1 to 3 substituents independently selected from halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy and benzyloxy; (C₈₋₁₄ alkyl)carbonylamino or (C₈₋₁₄ alkoxy)carbonylamino, R₂ is C₁₋₄ alkoxy or 2-(C₁₋₄ alkoxy)ethoxy, R₃ is hydrogen, C₁₋₄ alkyl, 2-(C₈₋₁₄ alkoxy)carbonylethyl, 2-(C₈₋₁₄ alkyl)carbonyloxyethyl or 2-(C₈₋₁₄ alkoxy)carbonyloxyethyl, and R₄ is hydrogen, C₁₋₄ alkyl, 2-cyanoethyl, 2-(C₁₋₃ alkoxy)ethyl, 2-(C₁₋₄ alkyl)carbonyloxyethyl, 2-(C₁₋₄ alkoxy)carbonylethyl, 2-(C₁₋₄ alkoxy)carbonyloxyethyl, C₃₋₄ alkenyl, ##STR27## 2-(C₈₋₁₄ alkyl)carbonyloxyethyl, 2-(C₈₋₁₄ alkoxy)carbonylethyl or 2-(C₈₋₁₄ alkoxy)carbonyloxyethyl,wherein R₅ is C₁₋₄ alkyl, allyl, (C₁₋₃ alkyl)carbonyl, phenyl or phenyl substituted by 1 to 3 substituents independently selected from halo, C₁₋₂ alkyl and C₁₋₂ alkoxy, and R₆ is hydrogen, C₁₋₄ alkyl or (C₁₋₃ alkyl)carbonyl, with the proviso that one and only one of R₁, R₃ and R₄ contains a C₈₋₁₄ alkyl moiety.
 14. A textile substrate according to claim 13 whereinD is ##STR28## wherein R₇ is hydrogen, cyano or halo,R₈ is hydrogen or chloro, R₉ is hydrogen or chloro, with the proviso that at least one of R₈ and R₉ is hydrogen, R₁₀ is cyano or nitro, R₁₂ is formyl, cyano, nitro, (C₁₋₄ alkoxy)carbonyl or (C₁₋₄ alkyl)carbonyl, R₁₃ is hydrogen, chloro, C₁₋₃ alkyl or phenyl, and R₁₄ is cyano, nitro or (C₁₋₄ alkoxy)carbonyl.
 15. A textile substrate according to claim 14 wherein D is ##STR29##
 16. A textile substrate according to claim 15 whereinD is ##STR30## wherein R₇ ' is chloro or bromo.
 17. A textile substrate according to claim 16 whereinR₁ is hydrogen; C₁₋₂ alkyl; C₁₋₂ alkoxy; formylamino; (C₁₋₄ alkyl)carbonylamino; (C₁₋₄ alkyl)carbonylamino the alkyl group of which is monosubstituted by halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy or benzyloxy; (C₂₋₄ alkenyl)carbonylamino; halo(C₂₋₄ alkenyl)carbonylamino; benzoylamino; benzoylamino the phenyl group of which is monosubstituted by halo, C₁₋₄ alkyl or C₁₋₄ alkoxy; (C₁₋₄ alkoxy)carbonylamino; (C₁₋₄ alkoxy)carbonylamino the alkyl moiety of which is monosubstituted by halo, C₁₋₃ alkoxy, cyano, phenyl, phenoxy or benzyloxy; (C₈₋₁₄ alkyl)carbonylamino or (C₈₋₁₄ alkoxy)carbonylamino, and R₅ is C₁₋₄ alkyl, allyl, (C₁₋₃ alkyl)carbonyl, phenyl or phenyl monosubstituted by halo, C₁₋₂ alkyl or C₁₋₂ alkoxy.
 18. A textile substrate according to claim 17 whereinR₁ is (C₁₋₂ alkyl)carbonylamino, R₂ is C₁₋₂ alkoxy or 2-(C₁₋₂ alkoxy)ethoxy, R₃ is hydrogen or C₁₋₄ alkyl, and R₄ is 2-(C₁₀₋₁₂ alkoxy)carbonylethyl.
 19. A textile substrate according to claim 13 comprising a linear aromatic polyester, cellulose 21/2 acetate, cellulose triacetate or a synthetic polyamide.
 20. A textile substrate according to claim 19 comprising a linear aromatic polyester. 